N,n&#39;-polynitroalky-oxamides



3,000,944- Patented Sept. 19, 1961 3,000,944 N,N'-POLYNITROALKY-0XAMIDES Milton B. Frankel, Pasadena, Calif., assignor to Aerojetgfilflal Corporation, Azusa, Calif., a corporation of No Drawing. Filed July 15, 1957, Ser. No. 672,541 15 Claims. (Cl. 260561) This invention relates to new compositions of matter and a method for their prepartion. In particular, this invention relates to polynitro nitramides having the general formula:

wherein R is an alkyl, nitro, or nitroalkyl radical, and A is an alkylene radical.

These compounds, due to their high oxygen content, find valuable use as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives in a device such as that disclosed in United States Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The compounds of this invention are prepared by nitrating the corresponding oxamides, in accordance with the general reaction scheme set forth below:

wherein A and R are as defined above.

Optimum results are obtained when a mixture of m'tric and sulfuric acid is employed as the nitrating reagent.

The oxamides useful as starting materials for this invention are readily obtained by the condensation of nitrocontaining amines with oxalyl compounds, as disclosed in my copending application No. 408,610, filed February 5, 1954, now abandoned.

To more clearly illustrate this invention, the following examples are presented. It is to be understood, however, that these examples are presented merely as a means of illustration and are not intended to limit the scope of the invention in any way.

EXAMPLE I Preparation of N ,N '-dinitr0-N,N '-bis(3,3,3- trinitropropyl) oxamide A 7.7 gm. quantity of N,N-bis(3,3,3-trinitropropyl) oxamide was added to a mixture of 75 ml. of concentrated sulfuric acid and 100 ml. of 100% nitric acid. The solution was warmed to 55 C., kept as this temperature for 20 minutes, cooled, and poured on ice. The white solid was collected, washed with water, and dried to yield 7.5 gm. (80.9%), M.P. 120-125 C. Three recrystallizations from chloroform gave white needles,

melting at 126-127 C., resolidifying at 128-129' C., and melting again at 130" C., I.S.=9 cm./2.5 kg. The elemental analysis of the product was as follows:

Calculated for c,H,N o,,= C, 18.05%; H, 1.52%; N, 26.32%. Found: C, 18.42%; H, 1.63%; N, 26.49%. Heat of combustion, AH Predicted: 1773 cal/g. Found: 1759 caL/g.

The explosive values of the product were:

Lead block value 126 T.N.T.= Ballistic mortar value 137 T.N.T.=100

EXAMPLE II Preparation of N,N'-dinitro N,N' bis(3,3- dinitrobutyl) oxamide N, 23.83%. Found: C, 25.84%; H, 3.26%; N, 24.37%.

The explosive values of the product were:

Lead block value 118 T.N.T.=100

Ballistic mortar value 129 T.N.T=100 As previously stated, optimum results are obtained when the nitration reaction of this invention is carried out using a mixture of nitric and sulfuric acid as the nitrating reagent. Other methods of nitration well known to those skilled in the art, such as those in which nitric acid, fuming nitric acid, etc. are employed as the nitrating reagents, are obviously within the scope of my invention.

Reaction temperature is not critical in the nitration reaction of this invention, the only effect of temperature variation being a corresponding increase or decrease in reaction rate.

I have also found that oxamides, such as N,N'-bis(3,3- clinitropentyl) oxamide, N,N'-bis(4,4,4-trinitrobutyl) oxamide, N,N'-bis(3,3-dinitrohexyl) oxamide, N,N'- his(3,3,5,5-tetranitrohexyl) oxamide, etc., readily undergo nitration in the presence of a mixture of nitric and sulfuric acid to form their corresponding polynitro nitramides, namely, N,N'-dinitro-N,N'-bis(3,3-dinitropentyl) oxamide, N,N'-dinitro-N,N'-bis(4,4,4-trinitrobutyl) oxamide, N,N'-dinitro-N,N-bis(3,3-dinitrohexyl) oxamide, N,N'-dinitro-N,N-bis( 3 ,3,5,5-tetranitrohexyl) oxamide, etc.

It is apparent that any member of this series of polynitro nitramides may be formed by merely nitrating an appropriate oxamide, in accordance with the teachings of this invention.

This application is a continuation-in-part of my copending United States patent application Serial No. 408,609, filed February 5, 1954, now abandoned.

I claim:

1. As compositions of matter, the polynitro nitramides having the formula:

wherein A is a lower alkylene radical and R is a radical selected from the group consisting of nitro, lower alkyl, and lower nitroalkyl radicals.

2. As compositions of matter, the polynitro nitramides having the formula:

wherein A is a lower alkylene radical.

3. As compositions of matter, the polynitro nitramides having the formula:

wherein A is a lower alkylene radical and R is a lower alkyl radical.

4. As compositions of matter, the polynitro nitramides having the formula:

bis(3,3-dinitrobuty1) oxamide having the structural formula:

t f? it w CHr?CH CHzN-C-G-N-JHiOHs- CH3 7. As a composition of matter, N,N'-dinitro-N,N'- bis(3,3,5,5-tetranitrohexyl) oxamide having the structural formula:

8. The method of preparing polynitro nitramides having the formula:

which comprises nitrating an aliphatic polynitro oxamide having the formula:

wherein A is a lower alkylene radical and R is a radical Cir 4 selected from a group consisting of nitro, lower alkyl, and lower nitroalkyl radicals.

9. The method of preparing polynitro nitramides having the formula:

which comprises nitrating an aliphatic polynitro oxamide having the formula:

wherein A is a lower alkylene radical.

10. The method of preparing polynitro nitramides having the formula:

which comprises nitrating an aliphatic polynitro oxamide having the formula:

wherein A is a lower alkylene radical and R is a lower alkyl radical.

11. The method of preparing polynitro nitramides having the formula:

N09 N01 (If E; i; No: R- .-A-1'-IC-0NA R NO: NO!

which comprises nitrating an aliphatic polynitro oxamide having the formula:

NO; Oi (f N02 wherein A is a lower alkylene radical and R is a lower nitroalkyl radical.

12. The method of claim 8 wherein the nitration is elfected by a mixture of nitric acid and sulfuric acid.

13. The method of preparing N,N'-dinitro-N,N'- bis(3,3,3-trinitropropyl) oxarnide which comprises re" acting N,N'-bis(3,3,3-trinitropropyl) oxamide with a mixture of sulfuric and nitric acid.

14. The method of preparing N,N'-dinitro-N,N'- bis(3,3-dinitrobutyl) oxamide which comprises reacting N,N'-bis(3,3-dinitrobutyl) oxamide with a mixture of sulfuric and nitric acid.

15. The method of preparing N,N-dinitro-N,N- bis(3,3,5,5-tetranitrohexyl) oxamide which comprises reacting N,N'-bis(3,3,5,5tetranithrohexyl) oxamide with a mixture of sulfuric and nitric acid.

No references cited. 

1. AS COMPOSITIONS OF MATTER, THE POLYNITRO NITRAMIDES HAVING THE FORMULA:
 9. THE METHOD OF PREPARING POLYNITRO NITRAMIDES HAVING THE FORMULA: 